JP2003335869A - Masterbatch for polypropylene resin and its use - Google Patents
Masterbatch for polypropylene resin and its useInfo
- Publication number
- JP2003335869A JP2003335869A JP2002142501A JP2002142501A JP2003335869A JP 2003335869 A JP2003335869 A JP 2003335869A JP 2002142501 A JP2002142501 A JP 2002142501A JP 2002142501 A JP2002142501 A JP 2002142501A JP 2003335869 A JP2003335869 A JP 2003335869A
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- Prior art keywords
- resin
- masterbatch
- pigment
- polypropylene resin
- pigments
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリプロピレン系
樹脂用マスターバッチ、特に自動車部品材料または家電
部品材料であるゴム強化ポリプロピレン系樹脂用及び、
無機フィラー含有ポリプロピレン系樹脂用のマスターバ
ッチ、及び滞留色ムラの無い外観上の優れた成形品に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a masterbatch for polypropylene resin, particularly for a rubber-reinforced polypropylene resin which is a material for automobile parts or household electric appliance parts, and
The present invention relates to a masterbatch for an inorganic filler-containing polypropylene resin, and a molded product excellent in appearance with no retention color unevenness.
【０００２】[0002]
【従来の技術】近年の自動車部品材料には高剛性・高耐
衝撃性および寸法安定性が良好であり、かつ薄肉または
複雑な射出成形性を有するプロピレン系樹脂を基材とし
た複合樹脂が多く使用されている。この複合樹脂には物
性改良のため、プロピレン系樹脂の他にオレフィン系ゴ
ム成分やタルク等のフィラー成分が配合されていること
が多く、色相が白色化の傾向を有する。2. Description of the Related Art In recent years, many automotive parts materials are composite resins based on a propylene-based resin that has high rigidity, high impact resistance and dimensional stability, and has thin or complicated injection moldability. It is used. In order to improve the physical properties, this composite resin is often blended with a filler component such as an olefin rubber component or talc in addition to the propylene resin, and the hue tends to be white.
【０００３】そして、これらの複合樹脂の着色剤として
はドライカラー・ペーストカラー・リキッドカラー・マ
スターバッチ等が用いられているが、非汚染性・計量適
性・貯蔵安定性等の理由からマスターバッチが主流とな
っている。マスターバッチはキャリアとなるオレフィン
系ベース樹脂を中心に高濃度の顔料・分散剤・安定剤等
を配合し、混練機および押出機によりペレット状に作製
されたものである。一般にマスターバッチを未着色の被
着色樹脂で２０〜１００倍に希釈して射出等の成形が行
われる。Although dry colors, paste colors, liquid colors, master batches, etc. are used as colorants for these composite resins, master batches are used for reasons such as non-contamination, metering suitability and storage stability. It is the mainstream. The masterbatch is prepared by mixing a high-concentration pigment, a dispersant, a stabilizer and the like mainly with an olefinic base resin as a carrier, and making it into pellets by a kneader and an extruder. Generally, a master batch is diluted 20 to 100 times with an uncolored resin to be colored, and molding such as injection is performed.
【０００４】しかしながら、その高い希釈倍率のため、
マスターバッチと被着色樹脂とが射出成形機のシリンダ
ー内で十分に溶融混練されないまま射出成形され、成形
品に色ムラの欠陥が発生することがあった。これを解消
するため、数々の検討が行われた。例えば、ベース樹脂
関連では、ポリプロピレンを用いた高結晶性ポリプロピ
レン用着色剤組成物（特開平８−３２５４２３号公
報）、ポリプロピレンと直鎖状低密度ポリプロピレンを
併用したポリプロピレン系複合材料着色用マスターバッ
チ（特開平９−３０２０９９号公報）等が開示されてい
る。また、顔料関連では、鉄黒を含有する多成分顔料を
用いたポリオレフィン組成物（特公昭６２−１４５７６
号公報）、黒色顔料としてｐＨ２〜４で、かつ平均粒径
１５〜２５ｍμのチャンネルタイプカーボンブラックを
用いたポリプロピレン着色組成物（特公平６−２７２３
６号公報）等が開示されている。However, because of its high dilution factor,
The masterbatch and the resin to be colored were injection-molded in a cylinder of an injection molding machine without being sufficiently melted and kneaded, and a defect such as color unevenness might occur in the molded product. A number of studies were conducted to eliminate this. For example, regarding the base resin, a highly crystalline polypropylene colorant composition using polypropylene (JP-A-8-325423), a polypropylene-based composite material coloring masterbatch in which polypropylene and linear low-density polypropylene are used in combination ( JP-A-9-302099) and the like are disclosed. Further, regarding pigments, a polyolefin composition using a multi-component pigment containing iron black (Japanese Patent Publication No. 62-14576).
Gazette), a polypropylene coloring composition using a channel type carbon black having a pH of 2 to 4 and an average particle size of 15 to 25 mμ as a black pigment (Japanese Patent Publication No. 6-2723).
No. 6) is disclosed.
【０００５】また、被着色樹脂のポリプロピレン系複合
樹脂がオレフィン系ゴム成分やタルク等のフィラー成分
の配合により白色度が高くなっている場合、マスターバ
ッチで着色すると特に色ムラが目立ちやすかった。この
対策として、マスターバッチ中の顔料濃度を高くして隠
蔽性を増すことにより、色ムラを目立たなくさせる方法
が一般的に行われるようになった結果、通常の連続射出
成形においては成形品の色ムラの発生が大きく低減され
た。Further, when the polypropylene-based composite resin as the resin to be colored has a high whiteness due to the addition of a filler component such as an olefin rubber component or talc, color unevenness is particularly noticeable when colored with a masterbatch. As a countermeasure for this, a method of making the color unevenness inconspicuous by increasing the pigment concentration in the masterbatch to increase the hiding property is generally performed. The occurrence of color unevenness was greatly reduced.
【０００６】[0006]
【発明が解決しようとする課題】しかし、顔料高濃度化
マスターバッチを用いた場合、従来とは別な原因と考え
られる色ムラの問題が発生するようになった。その問題
とは、連続射出成形時には成形品に色ムラが発生しない
が、連続成形を一時中断し、材料を成形機中に充填した
まま（滞留）数分〜数十分が経過した後、成形を再開し
た場合、成形再開後２〜３ショット目以降から８ショッ
ト程度までの射出成形品に色ムラが発生することであっ
た。この色ムラを滞留色ムラといい、通常成形時の色ム
ラと区別している。連続射出成形中に成形機を一時的に
止めることは、休憩時間・金型交換・機械類の調整等の
理由からごく一般的に行われることであり、射出成形再
開の度に滞留色ムラのある外観不良品が発生すること
は、作業工程上極めて大きな問題であった。However, when a pigment-enriched masterbatch is used, a problem of color unevenness, which is considered to be a cause different from the conventional one, has occurred. The problem is that color unevenness does not occur in the molded product during continuous injection molding, but after the continuous molding is temporarily interrupted and the material is filled in the molding machine (retention) for several minutes to several tens of minutes, However, the color unevenness was generated in the injection-molded article from the second to third shots and up to about eight shots after the restart of the molding. This color unevenness is called retention color unevenness and is distinguished from color unevenness during normal molding. Temporarily stopping the molding machine during continuous injection molding is very common due to reasons such as break times, mold replacement, and machine adjustments. Occurrence of a certain defective appearance was a very serious problem in the working process.
【０００７】この滞留色ムラの原因は不明であるが、通
常成形の色ムラを解消するためにマスターバッチの顔料
高濃度化が行われたため、成形機内において顔料が高濃
度状態で滞留し、表面特性の異なる顔料相互間の反発作
用が大きくなって顔料が分離（色別れ）することが一つ
の原因と考えられる。この現象は、二酸化チタンを併用
している場合、更に顕著に現れる。樹脂を着色する場
合、経済性と着色力に優れている点から黒色成分として
一般にカーボンブラックが用いられているが、このカー
ボンブラックは他の顔料に比べて粒子サイズが小さく、
同一の反発作用に於いても大きな影響を受け、色別れを
起こしやすく、滞留色ムラの大きな要因であると考えら
れている。この対策として、カーボンブラックの粒子径
を大きいものへの変更や、鉄黒顔料への変更をしてきた
が、より滞留色ムラ性に優れたマスターバッチとするた
めに、ベース樹脂の検討をおこなった。Although the cause of the retained color unevenness is unknown, the pigment in the masterbatch is usually made to have a high concentration in order to eliminate the color unevenness in the molding. It is considered that one of the causes is that the repulsive action between pigments having different characteristics becomes large and the pigments are separated (color separation). This phenomenon becomes more remarkable when titanium dioxide is used together. When coloring a resin, carbon black is generally used as a black component from the viewpoint of excellent economy and coloring power, but this carbon black has a smaller particle size than other pigments,
Even if the same repulsive action is exerted, a large influence is exerted, color separation easily occurs, and it is considered to be a major cause of retention color unevenness. As a countermeasure for this, we have changed the carbon black to a larger particle size and changed to iron black pigment, but in order to make a masterbatch with more excellent retention color unevenness, we examined the base resin. .
【０００８】マスターバッチのベース樹脂は、成形品の
物性保持の点では、ポリプロピレン系樹脂のみを用いる
ことが望ましいが、顔料の高濃度化や被着色樹脂への色
ムラを考慮し、ポリプロピレンとポリエチレンの併用配
合となっている。ポリエチレンの種類と流動性によっ
て、顔料及びその分散剤との相溶性が異なり、従来で
は、通常成形及び滞留時の色ムラに関し、両者のバラン
スのとれたマスターバッチが無かった。As the base resin of the masterbatch, it is desirable to use only a polypropylene resin from the viewpoint of maintaining the physical properties of the molded product, but polypropylene and polyethylene are used in consideration of the high concentration of the pigment and the color unevenness of the resin to be colored. It is a combination combination of. The compatibility with the pigment and its dispersant varies depending on the type and flowability of polyethylene, and conventionally, there was no masterbatch that normally balances color unevenness during molding and retention.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記問題
を解決すべく、マスターバッチのベース樹脂に特定のポ
リプロピレン系樹脂と低密度ポリエチレンを使用するこ
とで、成形途中での滞留後にも色ムラの発生しない成形
品が得られた。すなわち第１の発明は、
（Ａ）ポリプロピレン系樹脂（ＭＦＲ：１０ｇを超えか
つ２００ｇ未満の値／１０分 ２３０℃ ２．１６ｋｇ
荷重）
（Ｂ）低密度ポリエチレン樹脂（ＭＦＲ：２ｇを超えか
つ３０ｇ未満の値／１０分 １９０℃ ２．１６ｋｇ荷
重）
（Ｃ）ポリオレフィン系ワックス
（Ｄ）二酸化チタン顔料
（Ｅ）カーボンブラック、鉄黒顔料から選ばれる一種以
上の黒色顔料
（Ｆ）その他の多成分顔料
（Ａ）から（Ｆ）よりなるポリプロピレン系樹脂用マス
ターバッチである。In order to solve the above-mentioned problems, the present inventors have used a specific polypropylene resin and low density polyethylene as a base resin of a masterbatch so that they can be retained even during molding. A molded product with no color unevenness was obtained. That is, the first invention is (A) polypropylene-based resin (MFR: value of more than 10 g and less than 200 g / 10 minutes 230 ° C. 2.16 kg
Load) (B) Low density polyethylene resin (MFR: value of more than 2 g and less than 30 g / 10 minutes 190 ° C. 2.16 kg load) (C) Polyolefin wax (D) Titanium dioxide pigment (E) Carbon black, iron black A masterbatch for polypropylene resin, comprising one or more black pigments (F) selected from pigments and other multi-component pigments (A) to (F).
【００１０】第２の発明は、第１の発明に記載のポリプ
ロピレン系樹脂用マスターバッチを用いて成る成形品で
ある。A second invention is a molded product formed by using the polypropylene-based resin masterbatch according to the first invention.
【００１１】第３の発明は、ポリプロピレン樹脂成形品
の滞留色ムラの抑制方法である。A third invention is a method for suppressing the retention color unevenness of a polypropylene resin molded product.
【００１２】[0012]
【発明の実施の形態】以下、本発明を詳細に記載する。
本発明で用いられるポリプロピレン系樹脂（Ａ）として
は、結晶性または非晶性ポリプロピレン、エチレン−プ
ロピレンランダム共重合体、エチレン−プロピレンブロ
ック共重合体等が挙げられる。これらは１種、または２
種以上の併用系で使用することも出来る。また、ポリプ
ロピレン系樹脂（Ａ）のＭＦＲが１０以下ではマスター
バッチの被着色樹脂への分配性が悪くなり、ＭＦＲが２
００以上ではマスターバッチの生産時に加工が困難にな
る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
Examples of the polypropylene-based resin (A) used in the present invention include crystalline or amorphous polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer and the like. These are one or two
It is also possible to use a combination system of two or more species. When the MFR of the polypropylene resin (A) is 10 or less, the dispersibility of the masterbatch into the resin to be colored becomes poor, and the MFR is 2 or less.
When it is 00 or more, it becomes difficult to process the masterbatch during production.
【００１３】本発明で用いられる低密度ポリエチレン
（Ｂ）は、一般に原料エチレンを高温高圧下で、ラジカ
ル反応にて重合されるものである。低密度ポリエチレン
（Ｂ）は単純な長鎖ではなく、分子鎖の中間または端鎖
において短鎖または長鎖の分枝を生じていたり２重結合
があったりしてもよい。また、低密度ポリエチレン
（Ｂ）のＭＦＲが２以下ではマスターバッチの被着色樹
脂への分配性が悪くなり、ＭＦＲが３０以上では滞留色
ムラの改善効果が少ない。低密度ポリエチレン（Ｂ）の
代わりに直鎖状低密度ポリエチレンを使用すると滞留後
の成形時に色ムラが生じやすくなる。The low density polyethylene (B) used in the present invention is generally obtained by polymerizing ethylene as a raw material by a radical reaction under high temperature and high pressure. The low-density polyethylene (B) is not a simple long chain, and may have a short-chain or long-chain branch or a double bond in the middle or end of the molecular chain. When the MFR of the low-density polyethylene (B) is 2 or less, the distributability of the masterbatch to the resin to be colored is poor, and when the MFR is 30 or more, the effect of improving the retention color unevenness is small. When linear low-density polyethylene is used instead of low-density polyethylene (B), color unevenness is likely to occur during molding after retention.
【００１４】ポリプロピレン系樹脂用着色組成物におけ
るポリプロピレン系樹脂（Ａ）と低密度ポリエチレン
（Ｂ）が２：１〜１：２の配合比率の場合、被着色樹脂
への物性の影響、滞留色ムラの効果の点で好ましい。When the polypropylene resin (A) and the low-density polyethylene (B) in the polypropylene resin coloring composition have a mixing ratio of 2: 1 to 1: 2, the influence of the physical properties on the resin to be colored and the retention color unevenness are observed. It is preferable in terms of the effect.
【００１５】また、ポリプロピレン系樹脂用着色組成物
におけるポリプロピレン系樹脂（Ａ）と低密度ポリエチ
レン（Ｂ）とから成る樹脂成分の合計の配合量は、３０
〜６０重量％が好ましく、４０〜５０重量％が更に好ま
しい。配合割合が３０重量％未満ではマスターバッチの
形状をとれないおそれがあり、６０重量％を超えて配合
すると、相対的に顔料含有量が少なくなるので着色能が
低下し、成形品に色ムラが出るおそれがある。Further, the total amount of the resin components composed of the polypropylene resin (A) and the low density polyethylene (B) in the polypropylene resin coloring composition is 30.
-60% by weight is preferable, and 40-50% by weight is more preferable. If the blending ratio is less than 30% by weight, the shape of the masterbatch may not be obtained. If the blending ratio exceeds 60% by weight, the pigment content is relatively small and thus the coloring ability is lowered, resulting in color unevenness in the molded product. May come out.
【００１６】本発明で用いられるポリオレフィン系ワッ
クス（Ｃ）とは、結晶性または非晶性ポリプロピレンワ
ックス、低密度または高密度ポリエチレンワックス、エ
チレン−プロピレンランダム共重合体ワックス、エチレ
ン−プロピレンブロック共重合体ワックス、αオレフィ
ンとエチレンあるいはプロピレンの共重合体ワックス、
パラフィンワックス、カルナバワックス等が挙げられ
る。また、これらは１種、または２種以上の併用系で使
用することも出来る。The polyolefin wax (C) used in the present invention means crystalline or amorphous polypropylene wax, low density or high density polyethylene wax, ethylene-propylene random copolymer wax, ethylene-propylene block copolymer. Wax, copolymer wax of α-olefin and ethylene or propylene,
Examples include paraffin wax and carnauba wax. Further, these may be used alone or in combination of two or more.
【００１７】一般に樹脂を着色する場合、所望する色に
応じて数種類の顔料が用いられ、濃黒色以外は二酸化チ
タン（Ｄ）を用いて着色力を高めている。二酸化チタン
顔料（Ｄ）と黒色顔料（Ｅ）以外の顔料を本発明では多
成分顔料（Ｆ）という。In general, when coloring a resin, several kinds of pigments are used according to a desired color, and titanium dioxide (D) is used except for dark black to enhance the coloring power. Pigments other than the titanium dioxide pigment (D) and the black pigment (E) are referred to as multicomponent pigments (F) in the present invention.
【００１８】本発明では、黒色顔料（Ｄ）として一般的
にカラー用として平均粒子径が１５〜１００ｍμの範囲
にあるカーボンブラックまたは鉄黒顔料（酸化鉄）が用
いられる。製法に特定はなく一般に購入できるものでよ
い。カーボンブラックは、平均粒子径が大きい方が二酸
化チタン併用下での色別れを起こしにくくなるが、着色
力が低下するため、添加量の増加をまねきコストアップ
の傾向がある。鉄黒顔料は色別れの抑制に優れるが、カ
ーボンブラックに比べ着色力が５〜７分の１ほどしかな
く、色相・コストよっては使用が出来ないことが多い。In the present invention, as the black pigment (D), carbon black or iron black pigment (iron oxide) having an average particle diameter of 15 to 100 mμ is generally used for color. There is no specific manufacturing method, and it can be purchased generally. Carbon black having a larger average particle diameter is less likely to cause color separation when used in combination with titanium dioxide, but has a tendency to increase the amount added and increase the cost because the coloring power decreases. Although iron black pigments are excellent in suppressing color separation, they have a coloring power of only about 5 to 1/7 that of carbon black, and cannot be used in many cases depending on hue and cost.
【００１９】従来、本発明に記載のような、平均粒子径
の大きいカーボンブラックや鉄黒は着色力が低いため、
所望する色にするために相当量添加する必要があった。
しかし、これは経費がかかる上にマスターバッチの形状
が保てない恐れがあった。仮にマスターバッチ化が可能
であっても、このマスターバッチにより着色された成形
品は色ムラの問題を避けられず、顔料濃度が高いマスタ
ーバッチ作成の技術分野では非実用的なものであった。Conventionally, carbon black or iron black having a large average particle size as described in the present invention has a low coloring power,
It was necessary to add a considerable amount in order to obtain the desired color.
However, this is expensive and there is a risk that the shape of the masterbatch cannot be maintained. Even if it could be made into a masterbatch, the molded product colored by this masterbatch cannot avoid the problem of color unevenness, and it was impractical in the technical field of preparing a masterbatch with a high pigment concentration.
【００２０】本発明の構成により、黒色顔料を特定しな
くても色ムラが生じない、着色状態の良好な成形品の提
供が出来るようになった。更に、射出成形機内での滞留
時に他の顔料から反発作用を受けた場合にも色別れを起
こし難くなり、結果的に成形品の滞留色ムラの問題が解
消されたと考えられる。With the constitution of the present invention, it is possible to provide a molded product having a good coloring state in which color unevenness does not occur without specifying a black pigment. Furthermore, it is considered that color separation is less likely to occur even when the pigment is repelled by other pigments during retention in the injection molding machine, and as a result, the problem of uneven retention color of the molded product is solved.
【００２１】本発明で用いられる多成分顔料（Ｆ）のう
ち、二酸化チタン顔料（Ｄ）と黒色顔料（Ｅ）以外の顔
料は、従来からポリオレフィン系樹脂の着色に使用され
ている公知の顔料が使用できる。このような顔料の例と
しては、アゾ系・アントラキノン系・フタロシアニン系
・キナクリドン系・イソインドリノン系・ジオキサン系
・ペリレン系・キノフタロン系・ペリノン系等の有機顔
料や、酸化チタン・チタンイエロー・群青・コバルトブ
ルー・複合系酸化物顔料等の無機顔料が挙げられる。こ
れらの顔料の１種以上、または有機、無機を問わず２種
以上の組み合わせで黒色顔料（Ｅ）と共に用いられる。Among the multi-component pigments (F) used in the present invention, the pigments other than the titanium dioxide pigment (D) and the black pigment (E) are the well-known pigments conventionally used for coloring polyolefin resins. Can be used. Examples of such pigments include azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, dioxane-based, perylene-based, quinophthalone-based, perinone-based organic pigments, titanium oxide, titanium yellow, and ultramarine blue. -Inorganic pigments such as cobalt blue and complex oxide pigments are included. One or more of these pigments, or a combination of two or more of organic and inorganic pigments, is used together with the black pigment (E).
【００２２】ポリプロピレン系樹脂用マスターバッチに
おけるポリオレフィン系ワックス（Ｃ）、二酸化チタン
顔料（Ｄ）、黒色顔料（Ｅ）と多成分顔料（Ｆ）とから
成る顔料・分散剤成分の合計量は４０〜７０重量％が好
ましい。４０重量％未満では着色能が低下し、成形品に
色ムラが出るおそれがあり、７０重量％を超えるとマス
ターバッチとしての形状がとれないおそれがある。ま
た、（Ｃ）と、（Ｄ）＋（Ｅ）＋（Ｆ）の配合比率は
１：１〜１０であることが好ましい。The total amount of the pigment / dispersant component consisting of the polyolefin wax (C), the titanium dioxide pigment (D), the black pigment (E) and the multi-component pigment (F) in the master batch for polypropylene resin is 40 to 40. 70% by weight is preferred. If it is less than 40% by weight, the coloring ability may be deteriorated and the molded product may have uneven color, and if it exceeds 70% by weight, the shape of the master batch may not be obtained. Further, the mixing ratio of (C) and (D) + (E) + (F) is preferably 1: 1-10.
【００２３】本発明のポリオレフィン樹脂用着色組成物
は、通常の方法に従って加熱溶融して製造される。すな
わちバンバリーミキサー、ニーダー、ロール等の混練装
置で前述のポリオレフィンワックス（Ｃ）と二酸化チタ
ン（Ｄ）と黒色顔料（Ｅ）と多成分顔料（Ｆ）を含有す
る低密度ポリエチレン樹脂（Ｂ）を溶融混練し、次いで
この混練物とポリプロピレン樹脂（Ａ）とを押出機にて
溶融混練して粒状、円柱状、又は角状等に加工される。The coloring composition for polyolefin resin of the present invention is produced by heating and melting according to a usual method. That is, the low-density polyethylene resin (B) containing the above-mentioned polyolefin wax (C), titanium dioxide (D), black pigment (E) and multi-component pigment (F) is melted with a kneading device such as a Banbury mixer, a kneader and a roll. After kneading, the kneaded product and the polypropylene resin (A) are melt-kneaded by an extruder to be processed into particles, cylinders, or squares.
【００２４】本発明の成形品としては自動車部品材料、
家電部品材料等のプラスチック製品が挙げられる。尚、
本発明のポリオレフィン樹脂用マスターバッチには、本
発明の効果を阻害しない範囲で必要に応じて酸化防止
剤，紫外線吸収剤、安定剤、可塑剤、帯電防止剤、難燃
剤、充填剤、補強剤、界面活性剤、カップリング剤、造
核剤等の各種の添加剤を添加することもできる。The molded article of the present invention is an automobile part material,
Examples include plastic products such as materials for home electric appliances. still,
In the masterbatch for polyolefin resin of the present invention, an antioxidant, an ultraviolet absorber, a stabilizer, a plasticizer, an antistatic agent, a flame retardant, a filler, and a reinforcing agent are added to the masterbatch for the polyolefin resin, if necessary, within a range not impairing the effects of the present invention. Various additives such as a surfactant, a coupling agent, and a nucleating agent can also be added.
【００２５】本発明の成形品は、顔料濃度の高い上記ポ
リプロピレン樹脂用マスターバッチと未着色の被着色樹
脂（希釈樹脂）とを溶融混練後、射出成形して得られ
る。未着色の被着色樹脂としては、ポリプロピレン樹脂
用マスターバッチの基材樹脂であるポリプロピレン系樹
脂（Ａ）と同一のもの、またはこれと相溶性の良いもの
が用いられる。The molded article of the present invention is obtained by melt-kneading the above-mentioned polypropylene resin masterbatch having a high pigment concentration and an uncolored resin to be colored (diluting resin), and then injection molding. As the uncolored resin to be colored, the same resin as the polypropylene resin (A) which is the base resin of the masterbatch for polypropylene resin, or a resin having a good compatibility therewith is used.
【００２６】本発明の成形品は、必要に応じて酸化防止
剤，紫外線吸収剤、安定剤、可塑剤、帯電防止剤、難燃
剤、ゴム、タルク等の充填剤、補強剤、界面活性剤、カ
ップリング剤、造核剤等の各種の添加剤を添加すること
もできる。The molded article of the present invention contains, if necessary, antioxidants, ultraviolet absorbers, stabilizers, plasticizers, antistatic agents, flame retardants, rubbers, fillers such as talc, reinforcing agents, surfactants, Various additives such as a coupling agent and a nucleating agent can also be added.
【００２７】本発明の成形品は、顔料の含有濃度にもよ
るがマスターバッチを未着色のポリプロピレン系被着色
樹脂で２０〜１００倍に希釈するのが望ましい。２０倍
未満であると成形品の物性低下の恐れがあり、また、１
００倍を超えると色ムラの恐れがあるので好ましくな
い。In the molded article of the present invention, it is desirable to dilute the masterbatch 20 to 100 times with an uncolored polypropylene resin to be colored, depending on the content concentration of the pigment. If it is less than 20 times, the physical properties of the molded product may be deteriorated.
If it exceeds 00 times, color unevenness may occur, which is not preferable.
【００２８】[0028]
エチレンプロピレン共重合体樹脂−１（ＭＦＲ：３０、密度：０．９１） ２３ 重量％ 低密度ポリエチレン−２（ＭＦＲ：１０、密度：０．９２） ２３重量％ ポリエチレンワックス（分子量：４３００、密度：０．９２） １６．９重量％ 二酸化チタン（Ｐｉｇｍｅｎｔ Ｗｈｉｔｅ ６） ２３重量％ カーボンブラック（平均粒子径：２４ｍμ Ｐｉｇｍｅｎｔ Ｂｌａｃｋ ７） １重量％ 赤色酸化鉄（Ｐｉｇｍｅｎｔ Ｒｅｄ １０１） ２重量％ 黄色酸化鉄（Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １１９） １１重量％ フェノール系酸化防止剤（分子量：１１７８） ０．１重量％ Ethylene propylene copolymer resin-1 (MFR: 30, density: 0.91) 23 weight% Low density polyethylene-2 (MFR: 10, density: 0.92) 23% by weight Polyethylene wax (molecular weight: 4300, density: 0.92) 16.9% by weight Titanium dioxide (Pigment White 6) 23% by weight Carbon black (average particle size: 24 mμ Pigment Black 7) 1% by weight Red iron oxide (Pigment Red 101) 2% by weight Yellow Iron Oxide (Pigment Yellow 119) 11% by weight Phenolic antioxidant (Molecular weight: 1178) 0.1% by weight
【００２９】（マスターバッチの作製）まず、上記配合
比率の二酸化チタン、カーボンブラック、赤色酸化鉄、
黄色酸化鉄およびポリエチレンワックスを高速ミキサー
で混合した後、加圧ニーダーにて加熱溶融混練し、続い
て加熱三本ロールにて顔料分散処理を行い顆粒状または
粉体状の混練物を作製した。この混練物とエチレンプロ
ピレン共重合体樹脂−１、低密度ポリエチレン−１およ
び酸化防止剤を上記記載の比率で配合し、単軸スクリュ
ー押出機（Ｌ／Ｄ＝２５）にて温度２１０℃で溶融混練
を行い、押出されたストランドをペレタイザーにより長
さ２〜３ｍｍ・直径２〜３ｍｍの円筒状にカッティング
して、目的とするマスターバッチを得た。(Preparation of Masterbatch) First, titanium dioxide, carbon black, red iron oxide, and
After mixing the yellow iron oxide and the polyethylene wax with a high-speed mixer, the mixture was heated and melted and kneaded with a pressure kneader, and then the pigment was dispersed with a heating three-roll to prepare a granular or powdery kneaded product. This kneaded product, ethylene propylene copolymer resin-1, low density polyethylene-1 and antioxidant were blended in the above-mentioned ratio, and melted at a temperature of 210 ° C. in a single screw extruder (L / D = 25). Kneading was performed, and the extruded strand was cut into a cylindrical shape having a length of 2 to 3 mm and a diameter of 2 to 3 mm by a pelletizer to obtain a target masterbatch.
【００３０】（マスターバッチ生産性評価）マスターバ
ッチのペレット化が問題なく行えた場合をＯＫ、問題が
あった場合をＮＧとした。(Evaluation of Masterbatch Productivity) The case where pelletization of the masterbatch was carried out without any problems was judged to be OK, and the case where there was a problem was judged to be NG.
【００３１】（成形品の作製）上記マスターバッチ３重
量部と、被着色樹脂としてタルク２０％を含有するエチ
レン−プロピレンブロック共重合体１００重量部（ＭＦ
Ｒ：２５、密度：１．０４）とをタンブラーで混合し、
射出成形機（フルフライトスクリュー、Ｌ／Ｄ＝２４,
１００トン）で成形温度２２０℃、背圧１０ｋｇ／ｃｍ
2 にてプレート（１５０ｍｍ×３００ｍｍ×厚み２ｍ
ｍ）の連続成形を開始し、５ショット分のプレートを採
取（通常成形）した。次に、成形作業を３０分間停止
（材料は充填状態、温度は２２０℃を維持）し、その
後、停止前と同一条件で連続成形を再開して成形開始後
１〜５ショット目までの５枚のプレートを採取（滞留後
成形）した。(Production of molded article) 3 parts by weight of the above masterbatch and 100 parts by weight of ethylene-propylene block copolymer containing 20% of talc as a resin to be colored (MF).
R: 25, density: 1.04) are mixed with a tumbler,
Injection molding machine (full flight screw, L / D = 24,
100 tons) molding temperature 220 ° C, back pressure 10 kg / cm
Plate at 2 (150 mm x 300 mm x thickness 2 m
The continuous molding of m) was started, and plates for 5 shots were sampled (normal molding). Next, the molding operation is stopped for 30 minutes (the material is in a filled state and the temperature is maintained at 220 ° C.), and then continuous molding is restarted under the same conditions as before the stop, and 5 sheets from the first shot to the fifth shot after the start of molding. The plate was collected (molded after staying).
【００３２】（分配性の評価）通常成形（連続成形）時
のプレート５枚と、成形再開（滞留後成形）時のプレー
ト５枚の表面色ムラの状態を目視観察した。各プレート
を以下に示す５段階の基準で評価し５枚の平均値を＜表
−３＞に示した。
◎ ： 色ムラ無く、通常成形と同等
○ ： 僅かに色ムラ有り
△ ： 部分的に色ムラ有り
△〜×： 部分的に目立つ色ムラ有り
× ： 全体に色ムラ有り
△以上を合格とした。(Evaluation of Distributability) The state of surface color unevenness of 5 plates during normal molding (continuous molding) and 5 plates after restarting molding (molding after retention) was visually observed. Each plate was evaluated on the basis of the following 5 grades, and the average value of 5 plates is shown in Table 3. ◎: No color unevenness, equivalent to normal molding ○: Slightly color unevenness △: Partially color unevenness △ to ×: Partially noticeable color unevenness ×: Overall color unevenness △ or above: Passed.
【００３３】（機械物性評価）上記マスターバッチ３重
量部と、被着色樹脂としてタルク２０％を含有するエチ
レン−プロピレンブロック共重合体１００重量部（ＭＦ
Ｒ：２５、密度：１．０４）とをタンブラーで混合し、
射出成形機（フルフライトスクリュー、Ｌ／Ｄ＝２４、
１００トン）で成形温度２２０℃、背圧１０ｋｇ／ｃｍ
2にて物性試験片を作成した。曲げ試験 ＡＳＴ
Ｍ Ｄ７９０に、アイゾット試験 ＡＳＴＭ Ｄ２５６
に準じて実施し、マスターバッチを未添加のナチュラル
に対する保持率で表し、９５％以上を合格とした。(Evaluation of mechanical properties) 3 parts by weight of the above masterbatch and 100 parts by weight of ethylene-propylene block copolymer containing 20% of talc as a resin to be colored (MF)
R: 25, density: 1.04) are mixed with a tumbler,
Injection molding machine (full flight screw, L / D = 24,
100 tons) molding temperature 220 ° C, back pressure 10 kg / cm
A physical property test piece was prepared in 2 . Bending test AST
M D790, Izod test ASTM D256
The masterbatch was expressed by the retention rate with respect to non-added natural, and 95% or more was passed.
【００３４】〔実施例２〜実施例６〕、〔比較例１〜比
較例５〕
＜表−１＞、＜表−２＞に記載の配合で実施例１と同様
にマスターバッチを作成し評価を行い、結果を＜表−３
＞に示した。[Examples 2 to 6], [Comparative Examples 1 to 5] Master batches were prepared in the same manner as in Example 1 with the formulations shown in Tables 1 and 2 and evaluated. And the results are shown in <Table-3.
>.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】[0037]
【表３】 [Table 3]
【００３８】[0038]
【発明の効果】本発明のポリプロピレン系樹脂用マスタ
ーバッチは、（Ａ）ポリプロピレン系樹脂（ＭＦＲ：１
０ｇを超えかつ２００ｇ未満の値／１０分 ２３０℃
２．１６ｋｇ荷重）、（Ｂ）低密度ポリエチレン樹脂
（ＭＦＲ：２ｇを超えかつ３０ｇ未満の値／１０分 １
９０℃ ２．１６ｋｇ荷重）、（Ｃ）ポリオレフィン系
ワックス、（Ｄ）二酸化チタン顔料、（Ｅ）カーボンブ
ラック、鉄黒顔料から選ばれる一種以上の黒色顔料、
（Ｆ）その他の多成分顔料よりなるが、低密度ポリエチ
レン樹脂（Ｂ）の配合により分配性が高められる。従っ
て、表面特性の異なる顔料が共に配合されていても、成
形品の製造工程における顔料の分離（色別れ）を低減
し、成形品における色ムラ発生が減少する。The masterbatch for polypropylene resin of the present invention comprises (A) polypropylene resin (MFR: 1
Value greater than 0g and less than 200g / 10 minutes 230 ° C
2.16 kg load), (B) Low-density polyethylene resin (MFR: value of more than 2 g and less than 30 g / 10 min 1
90 ° C. 2.16 kg load), (C) polyolefin wax, (D) titanium dioxide pigment, (E) carbon black, one or more black pigments selected from iron black pigments,
(F) Other multi-component pigments, but the dispersibility is enhanced by blending the low density polyethylene resin (B). Therefore, even if pigments having different surface characteristics are blended together, the pigment separation (color separation) in the manufacturing process of the molded product is reduced, and the occurrence of color unevenness in the molded product is reduced.
【００３９】また、本発明のマスターバッチを用いて得
られる成形品は、被着色樹脂の白色度が高い場合やマス
ターバッチ中の顔料濃度が比較的低い場合でも色ムラが
目立ちにくい。さらに、連続射出成形を一時中断して
も、成形機中で顔料が色別れを起こさないので、成形品
に滞留色ムラが発生せず外観の優れた成形品が安定して
得られるので作業効率に優れる。Further, the molded product obtained by using the masterbatch of the present invention is less prominent in color unevenness even when the whiteness of the resin to be colored is high or the pigment concentration in the masterbatch is relatively low. In addition, even if the continuous injection molding is temporarily stopped, the pigments do not separate in the molding machine, so there is no uneven coloring in the molded product and a molded product with an excellent appearance can be obtained in a stable manner. Excellent in.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F070 AA12 AA13 AA15 AA63 AC04 AC13 AC15 AC94 AE02 AE04 AE09 FA03 FA07 FB03 FB06 FB07 FC01 FC03 4J002 AE033 BB03X BB033 BB053 BB12W BB15W BB153 BP03W DA037 DE136 FD096 FD097 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4F070 AA12 AA13 AA15 AA63 AC04 AC13 AC15 AC94 AE02 AE04 AE09 FA03 FA07 FB03 FB06 FB07 FC01 FC03 4J002 AE033 BB03X BB033 BB053 BB12W BB15W BB153 BP03W DA037 DE136 FD096 FD097
Claims (3)
０ｇを超えかつ２００ｇ未満の値／１０分 ２３０℃
２．１６ｋｇ荷重） （Ｂ）低密度ポリエチレン樹脂（ＭＦＲ：２ｇを超えか
つ３０ｇ未満の値／１０分 １９０℃ ２．１６ｋｇ荷
重） （Ｃ）ポリオレフィン系ワックス （Ｄ）二酸化チタン顔料 （Ｅ）カーボンブラック、鉄黒顔料から選ばれる一種以
上の黒色顔料 （Ｆ）その他の多成分顔料 （Ａ）から（Ｆ）よりなるポリプロピレン系樹脂用マス
ターバッチ。1. A polypropylene resin (A) (MFR: 1)
Value greater than 0g and less than 200g / 10 minutes 230 ° C
2.16 kg load) (B) Low density polyethylene resin (MFR: value of more than 2 g and less than 30 g / 10 minutes at 190 ° C. 2.16 kg load) (C) Polyolefin wax (D) Titanium dioxide pigment (E) Carbon black A masterbatch for polypropylene resin, which comprises one or more black pigments (F) selected from iron black pigments and other multi-component pigments (A) to (F).
用マスターバッチを用いて成る成形品。2. A molded product obtained by using the polypropylene-based resin masterbatch according to claim 1.
の抑制方法。3. A method for suppressing uneven retention color of a polypropylene resin molded product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002142501A JP2003335869A (en) | 2002-05-17 | 2002-05-17 | Masterbatch for polypropylene resin and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002142501A JP2003335869A (en) | 2002-05-17 | 2002-05-17 | Masterbatch for polypropylene resin and its use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003335869A true JP2003335869A (en) | 2003-11-28 |
Family
ID=29702768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002142501A Pending JP2003335869A (en) | 2002-05-17 | 2002-05-17 | Masterbatch for polypropylene resin and its use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003335869A (en) |
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